CN103172095A - Method for producing ultrawhite aluminum hydroxide and by-products from high-alumina fly ash by using high-temperature alkaline leaching - Google Patents
Method for producing ultrawhite aluminum hydroxide and by-products from high-alumina fly ash by using high-temperature alkaline leaching Download PDFInfo
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Abstract
The invention belongs to the technical field of metallurgy and in particular relates to a method for producing ultrawhite aluminum hydroxide and by-products from high-alumina fly ash by using high-temperature alkaline leaching. The method comprises the following steps of: carrying out two-stage pre-desilicication on the high-alumina fly ash, and then carrying out leaching reaction for 1.5-2.5 hours at 230-280 DEG C to respectively produce the ultrawhite hydroxide as well as wollastonite and ferrugination hydrogarnet as by-products. According to the method, a high-temperature sintering process in which low alumina-silica ratio firing temperature is difficult to control in the process of extracting aluminum hydroxide from the high-alumina fly ash is avoided, the energy consumption is reduced, the comprehensive utilization value of the fly ash is improved, and meanwhile, products in each link can be recycled in each procedure; and an economic and effective technical approach is provided for preparation of the ultrawhite aluminum hydroxide and alumina from the high-alumina fly ash.
Description
Technical field
The invention belongs to metallurgical technology field, be specifically related to a kind of method that aluminous fly-ash high temperature alkali soaks production ultrawhite aluminium hydroxide and byproduct.
Background technology
Fly ash is abundant, and output is concentrated greatly, every 1000Kwh electricity of power plant, and average generation flyash 87kg, along with the continuous increase of electricity needs, its quantity discharged also will increase year by year, and discarded flyash is land occupation both, again contaminate environment; And simultaneously, exhaustion day by day along with China and even worldwide bauxite resource, extract aluminum oxide from flyash, meet the industry policy that China develops a circular economy and builds a resource-conserving and environment-friendly society, become in recent years the focus that relevant industries are paid close attention to and studied.
Extract the common method of aluminum oxide from aluminous fly-ash alkaline process, acid system and using acid and alkali combination method are arranged.Wherein, alkaline process has limestone sintering method and soda-lime sintering process, traditional limestone sintering method is to take flyash as raw material, adopt the limestone sintering method to produce aluminum oxide, its key step comprises: the preparation of raw material and efflorescence, the leaching of aluminum oxide alkali lye, liquid-solid separation, alumina solution carbon divides, the bayer's process stripping, plant and divide, aluminium hydroxide separation and roasting and cement clinker calcination etc., limestone sintering method energy consumption high (1300~1400 ℃ of sintering temperatures), disposable consumed resource large (every processing 1t flyash consumes about 2.3t limestone resource), calcium silicate slag quantity discharged large (every processing 1t flyash produces approximately 3.2 t calcium silicate slags), pre-desiliconizing+soda-lime sintering process is that the aluminous fly-ash that utilizes of the international renewable resource of Inner Mongol Datang development corporation, Ltd. independent development extracts the technology of the silicon products such as aluminum oxide co-producing white carbon black, active calcium silicate, the principal feature of the method is to adopt the pre-desiliconizing technology, improve alumina silica ratio, be lowered into the quantity of slag, mainly comprise: the preparation of pre-desiliconizing, white carbon black (active calcium silicate), charge pulp preparation, grog burn till, one or two sections atmospheric silicon removing, carbon divide, kind is divided and the operation such as roasting, the improvement soda-lime sintering process is that the flyash that utilizes of the independent development such as specialized laboratory of The Chinese Geology Univ. (Beijing) mineral material country extracts the technology of aluminum oxide coproduction wollastonite, the method is that sintered material calcium has dropped to 1 than from 2 with the key distinction of Datang technique, reduced and burnt till energy consumption and become the quantity of slag, but above-mentioned soda-lime sintering process sintering reaction complexity, the solubility rate of aluminum oxide is not high.In acid system, more representational method is the sulfuric acid to leach method, and the method is: at first with the NH of finite concentration and volume
4f is soaked flyash as solubility promoter, then uses the H of finite concentration and volume
2sO
4dissolved at a certain temperature, Al is with Al
2(SO4)
3form from flyash, leached, add (NH after removing impurity F e
4)
2sO
4reaction generates NH with it
4al (SO
4)
212H
2o finally heats NH under 950 ℃
4al (SO
4)
212H
2o just can obtain Al
2o
3; Adopt at present the method for acidic process flyash to also have the salt acid system, the method is: the hydrochloric acid reaction that is 26% by flyash and concentration, keep temperature approximately under the condition of 100 ℃ 1~2 hour, obtain qualified dissolution fluid after filtering, separating, then evaporated and crystallization, crystallization aluminum chloride product, obtain alumina product by calcining, but a large amount of use severe corrosion equipments of acid, be difficult to realize large-scale industrial production, the technical process of using acid and alkali combination method is more complicated, and the consumption of alkali is large.
Summary of the invention
Problem utilization of fly ash existed for prior art, the invention provides a kind of method that aluminous fly-ash high temperature alkali soaks production ultrawhite aluminium hydroxide and byproduct, purpose is mode production ultrawhite aluminium hydroxide by-product wollastonite and the iron hibsehite soaked by flyash being carried out to two sections pre-desiliconizings and high temperature alkali, avoid the low alumina-silica ratio firing temperature restive high-temperature sintering process of aluminous fly-ash in extracting the aluminium hydroxide process, reduce energy consumption simultaneously, improve the comprehensive utilization value of flyash.
Realize that the technical scheme of the object of the invention carries out according to following steps:
(1) aluminous fly-ash is milled to below granularity 200 orders, mixes Al in mixed solution with circulation NaOH solution and tricalcium aluminate
20
3concentration is 13 ~ 14g/L, and α k=30 carries out one section atmospheric silicon removing 0.5 ~ 1.0h in 80 ~ 105 ℃
,obtain one section desiliconization liquid and one section desiliconization slag, then at 130 ~ 160 ℃, 0.27 under the condition of ~ 0.62MPa, one section desiliconization slag is carried out to pressure-off silicon 0.5 ~ 1.0h in two sections, obtain two-stage desilication slag and two-stage desilication liquid, one section desiliconization liquid is mixed with two-stage desilication liquid, in mixed desiliconization liquid, add milk of lime to carry out causticizing reaction, the add-on of milk of lime is 38 ~ 42% of desiliconization liquid volume after mixing, obtain the wollastonite slurries, to wollastonite slurries separating, washing, obtain solid silicon lime stone and NaOH solution, using the NaOH solution that obtains as circulation NaOH solution, with return to initial step and mix with flyash, to the solid silicon lime stone, add the milk of lime that accounts for solid silicon lime stone volume 5.0 ~ 8.0% to carry out dealkalize, then adopt the acetic acid pickling, after the control pickling, the wollastonite pH value is 6.9 ~ 7.1, stops 8 ~ 10h in 230 ~ 280 ℃ of insulations, then, after drying, obtains the wollastonite product,
(2) the two-stage desilication slag is mixed with circulating mother liquor, add ferrous acid sodium and milk of lime, in 230 ~ 280 ℃ of Leaching reaction 1.5 ~ 2.5h, to the leaching slurry obtained diluted, after separating, washing, obtain solid water garnet and dissolution fluid, after the solid water garnet is carried out to the separating, washing oven dry, obtain iron hibsehite product; Described ferrous acid sodium add-on control mode is: Fe in ferrous acid sodium
2o
3al in/two-stage desilication slag
2o
3mass ratio is (0.5 ~ 0.7): 1, and described milk of lime add-on control mode is: Al in CaO/ two-stage desilication slag in milk of lime
2o
3mass ratio is 2.0:1;
(3) add milk of lime in the dissolution fluid in step (2), in 180 ~ 185 ℃ of stripping reaction 1.0 ~ 1.5h, obtain the tricalcium aluminate slurries, the tricalcium aluminate slurries are carried out to solid-liquid separation, obtain tricalcium aluminate filter cake and tricalcium aluminate parting liquid, the tricalcium aluminate filter cake is washed, obtained tricalcium aluminate and tricalcium aluminate washing lotion; Described milk of lime add-on control mode is: Al in the CaO/ dissolution fluid in milk of lime
2o
3mass ratio is 1.5:1;
(4) tricalcium aluminate is mixed with the carbon mother liquid after evaporation, in 180 ~ 185 ℃ of reaction 1.0 ~ 1.5h, obtain calcium carbonate serosity, after the calcium carbonate serosity separating, washing, obtain calcium carbonate filter cake and parting liquid, in parting liquid, continue to pass into CO
2carry out the carbonating decomposition
,the carbonating obtained is decomposed slurries after filtering, obtains aluminum hydroxide filter cake and parting liquid, and filter cake, through washing, obtains aluminium hydroxide solid and aluminum hydroxide wash liquor, after the aluminium hydroxide solid is dried, obtains finished product ultrawhite aluminium hydroxide; Described CO
2the add-on control mode is: pass into CO
2al in/parting liquid
2o
3mass ratio is (1.2 ~ 1.4): 1.
Described tricalcium aluminate parting liquid and the tricalcium aluminate washing lotion mixing that accounts for tricalcium aluminate washing lotion cumulative volume 60 ~ 65%, NaOH concentration 260-280g/l in the evaporation control mixed solution, enter in step (2) and carry out Leaching reaction as circulating mother liquor; Remaining 35 ~ 40% tricalcium aluminate washing lotions are returned in step (1) and are mixed with aluminous fly-ash.
After mixing, the parting liquid that described carbonating decomposition slurries obtain after filtering and aluminum hydroxide wash liquor as carbon mother liquid, carbon mother liquid is evaporated to Na in solution
2cO
3concentration is 140 ~ 150g/l, obtains mother liquid evaporation and solid sodium carbonate, and described mother liquid evaporation returns in step (4) and mixes with tricalcium aluminate, and described solid sodium carbonate mixes with iron filings
,at Na
2cO
3/ Fe
2o
3weight ratio is (0.661 ~ 0.664): roasting under 1,800 ~ 900 ℃ of conditions, obtain ferrous acid sodium, and enter in step (2) and carry out Leaching reaction.
Described calcium carbonate filter cake adds in 90 ~ 100 ℃ of hot water after 950 ~ 1050 ℃ of lower roastings carries out lime slaking, is prepared into qualified milk of lime, enters in step (1), step (2) and step (3).
Compared with prior art, characteristics of the present invention and beneficial effect are:
The inventive method adopts two sections pre-desiliconizings and high temperature alkali soaking technology, effectively avoided available technology adopting high temperature sintering method to extract in aluminium hydroxide from aluminous fly-ash, cause the restive problem of firing temperature because alumina silica ratio in flyash is low, reached the reduction energy consumption, improve the purpose of the comprehensive utilization value of flyash, simultaneously the product of links can carry out the recycle of each flow process, for aluminous fly-ash prepares ultrawhite aluminium hydroxide and aluminum oxide provides a cost-effective technological approaches.
The aluminium hydroxide that the inventive method obtains is consumption maximum and most widely used inorganic fire-retarded additive, is widely used in the industries such as thermosetting resin, thermoplastics, synthetic rubber, coating and building materials; The wollastonite product is widely used in the industrial production such as automobile, metallurgy, pottery, plastics; The iron hibsehite can be used as the grog of producing cement, produce the starting material of brick, refractory materials, pedestrian trail board, decorating road material, the flux filler of ferrous metallurgy industry sintered material, the building area that mine working, coombe, mining site, salty soils etc. have rubbish again during farming as inert aggregate, and the properties-correcting agent of poor iron soil.
The inventive method not only can be used for processing aluminous fly-ash, also can be for the treatment of nepheline and Bayer process red mud, the inventive method not only can production ultrawhite aluminium hydroxide by-product wollastonite and iron hibsehite, also can produce other aluminium hydroxides and alumina article.
The accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
al in aluminous fly-ash described in the present invention
2o
3massfraction be 40 ~ 50%.
Embodiment 1
(1) aluminous fly-ash is milled to below granularity 200 orders, mixes Al in mixed solution with circulation NaOH solution and tricalcium aluminate washing lotion
20
3concentration is 13 ~ 14g/L, and α k=30 carries out one section atmospheric silicon removing 1.0h in 80 ℃
,obtain one section desiliconization liquid and one section desiliconization slag, then at 160 ℃, 0.27MPa condition under one section desiliconization slag is carried out to pressure-off silicon 0.8h in two sections, obtain two-stage desilication slag and two-stage desilication liquid, one section desiliconization liquid and two-stage desilication liquid are mixed to get to mixed solution, in mixed solution, add milk of lime to carry out causticizing reaction, the add-on of milk of lime is 38% of desiliconization liquid volume after mixing, obtain the wollastonite slurries, to wollastonite slurries separating, washing, obtain solid silicon lime stone and NaOH solution, using the NaOH solution that obtains as circulation NaOH solution, with return to initial step and mix with flyash, to the solid silicon lime stone, add the milk of lime that accounts for solid silicon lime stone volume 5.0% to carry out dealkalize, then adopt the acetic acid pickling, after the control pickling, the wollastonite pH value is 6.9, stops 8h in 280 ℃ of insulations, then, after drying, obtains the wollastonite product,
(2) the two-stage desilication slag is mixed with circulating mother liquor, add ferrous acid sodium and milk of lime, in 230 ℃ at Leaching reaction 2.5h, to the leaching slurry obtained diluted, after separating, washing, obtain solid water garnet and dissolution fluid, after the solid water garnet is carried out to the separating, washing oven dry, obtain iron hibsehite product; Described ferrous acid sodium add-on control mode is: Fe in ferrous acid sodium
2o
3al in/two-stage desilication slag
2o
3mass ratio is 0.5:1, and described milk of lime add-on control mode is: Al in CaO/ two-stage desilication slag in milk of lime
2o
3mass ratio is 2.0:1;
(3) add milk of lime in the dissolution fluid in step (2), in 180 ℃ of stripping reaction 1.5h, obtain the tricalcium aluminate slurries, the tricalcium aluminate slurries are carried out to solid-liquid separation, obtain tricalcium aluminate filter cake and tricalcium aluminate parting liquid, the tricalcium aluminate filter cake is washed, obtained tricalcium aluminate and tricalcium aluminate washing lotion; Described milk of lime add-on control mode is: Al in the CaO/ dissolution fluid in milk of lime
2o
3mass ratio is 1.5:1;
(4) tricalcium aluminate is mixed with the carbon mother liquid after evaporation, in 180 ℃ of reaction 1.5h, obtain calcium carbonate serosity, after the calcium carbonate serosity separating, washing, obtain calcium carbonate filter cake and parting liquid, in parting liquid, continue to pass into CO
2carry out the carbonating decomposition
,the carbonating obtained is decomposed slurries after filtering, obtains aluminum hydroxide filter cake and parting liquid, and filter cake, through washing, obtains aluminium hydroxide solid and aluminum hydroxide wash liquor, after the aluminium hydroxide solid is dried, obtains finished product ultrawhite aluminium hydroxide; Described CO
2the add-on control mode is: pass into CO
2al in/parting liquid
2o
3mass ratio is 1.2:1.
Described tricalcium aluminate parting liquid and the tricalcium aluminate washing lotion mixing that accounts for tricalcium aluminate washing lotion cumulative volume 60%, NaOH concentration 260g/l in the evaporation control mixed solution, enter in step (2) and carry out Leaching reaction as circulating mother liquor; Remaining 40% tricalcium aluminate washing lotion is returned in step (1) and is mixed with aluminous fly-ash.
After mixing, the parting liquid that described carbonating decomposition slurries obtain after filtering and aluminum hydroxide wash liquor as carbon mother liquid, carbon mother liquid is evaporated to Na in solution
2cO
3concentration is 140g/l, obtains mother liquid evaporation and solid sodium carbonate, and described mother liquid evaporation returns in step (4) and mixes with tricalcium aluminate, and described solid sodium carbonate mixes with iron filings, at Na
2cO
3/ Fe
2o
3weight ratio is 0.661:1, and roasting under 800 ℃ of conditions, obtain ferrous acid sodium, enters in step (2) and carries out Leaching reaction.
Described calcium carbonate filter cake adds in 100 ℃ of hot water after 950 ℃ of lower roastings carries out lime slaking, is prepared into qualified milk of lime, enters in step (1), step (2) and step (3).
Embodiment 2
(1) aluminous fly-ash is milled to below granularity 200 orders, mixes Al in mixed solution with circulation NaOH solution and tricalcium aluminate washing lotion
20
3concentration is 13 ~ 14g/L, and α k=30 carries out one section atmospheric silicon removing 0.8h in 90 ℃
,obtain one section desiliconization liquid and one section desiliconization slag, then at 130 ℃, 0.62MPa condition under one section desiliconization slag is carried out to pressure-off silicon 0.5h in two sections, obtain two-stage desilication slag and two-stage desilication liquid, one section desiliconization liquid and two-stage desilication liquid are mixed to get to mixed solution, in mixed solution, add milk of lime to carry out causticizing reaction, the add-on of milk of lime is 40% of desiliconization liquid volume after mixing, obtain the wollastonite slurries, to wollastonite slurries separating, washing, obtain solid silicon lime stone and NaOH solution, using the NaOH solution that obtains as circulation NaOH solution, with return to initial step and mix with flyash, to the solid silicon lime stone, add the milk of lime that accounts for solid silicon lime stone volume 5.0% to carry out dealkalize, then adopt the acetic acid pickling, after the control pickling, the wollastonite pH value is 7.0, stops 9h in 250 ℃ of insulations, then, after drying, obtains the wollastonite product,
(2) the two-stage desilication slag is mixed with circulating mother liquor, add ferrous acid sodium and milk of lime, in 250 ℃ at Leaching reaction 2h, to the leaching slurry obtained diluted, after separating, washing, obtain solid water garnet and dissolution fluid, after the solid water garnet is carried out to the separating, washing oven dry, obtain iron hibsehite product; Described ferrous acid sodium add-on control mode is: Fe in ferrous acid sodium
2o
3al in/two-stage desilication slag
2o
3mass ratio is 0.6:1, and described milk of lime add-on control mode is: Al in CaO/ two-stage desilication slag in milk of lime
2o
3mass ratio is 2.0:1;
(3) add milk of lime in the dissolution fluid in step (2), in 183 ℃ of stripping reaction 1.2h, obtain the tricalcium aluminate slurries, the tricalcium aluminate slurries are carried out to solid-liquid separation, obtain tricalcium aluminate filter cake and tricalcium aluminate parting liquid, the tricalcium aluminate filter cake is washed, obtained tricalcium aluminate and tricalcium aluminate washing lotion; Described milk of lime add-on control mode is: Al in the CaO/ dissolution fluid in milk of lime
2o
3mass ratio is 1.5:1;
(4) tricalcium aluminate is mixed with the carbon mother liquid after evaporation, in 185 ℃ of reaction 1.0h, obtain calcium carbonate serosity, after the calcium carbonate serosity separating, washing, obtain calcium carbonate filter cake and parting liquid, in parting liquid, continue to pass into CO
2carry out the carbonating decomposition
,the carbonating obtained is decomposed slurries after filtering, obtains aluminum hydroxide filter cake and parting liquid, and filter cake, through washing, obtains aluminium hydroxide solid and aluminum hydroxide wash liquor, after the aluminium hydroxide solid is dried, obtains finished product ultrawhite aluminium hydroxide; Described CO
2the add-on control mode is: pass into CO
2al in/parting liquid
2o
3mass ratio is 1.3:1.
Described tricalcium aluminate parting liquid and the tricalcium aluminate washing lotion mixing that accounts for tricalcium aluminate washing lotion cumulative volume 65%, NaOH concentration 270g/l in the evaporation control mixed solution, enter in step (2) and carry out Leaching reaction as circulating mother liquor; Remaining 35% tricalcium aluminate washing lotion is returned in step (1) and is mixed with aluminous fly-ash.
After mixing, the parting liquid that described carbonating decomposition slurries obtain after filtering and aluminum hydroxide wash liquor as carbon mother liquid, carbon mother liquid is evaporated to Na in solution
2cO
3concentration is 150g/l, obtains mother liquid evaporation and solid sodium carbonate, and described mother liquid evaporation returns in step (4) and mixes with tricalcium aluminate, and described solid sodium carbonate mixes with iron filings, at Na
2cO
3/ Fe
2o
3weight ratio is 0.664:1, and roasting under 900 ℃ of conditions, obtain ferrous acid sodium, enters in step (2) and carries out Leaching reaction.
Described calcium carbonate filter cake adds in 90 ℃ of hot water after 1050 ℃ of lower roastings carries out lime slaking, is prepared into qualified milk of lime, enters in step (1), step (2) and step (3).
Embodiment 3
(1) aluminous fly-ash is milled to below granularity 200 orders, mixes Al in mixed solution with circulation NaOH solution and tricalcium aluminate washing lotion
20
3concentration is 13 ~ 14g/L, α k=30, Al in mixed solution
2o
3concentration is 13 ~ 14g/L, and α k=30 carries out one section atmospheric silicon removing 0.5h in 105 ℃
,obtain one section desiliconization liquid and one section desiliconization slag, then at 150 ℃, 0.51MPa condition under one section desiliconization slag is carried out to pressure-off silicon 1.0h in two sections, obtain two-stage desilication slag and two-stage desilication liquid, one section desiliconization liquid and two-stage desilication liquid are mixed to get to mixed solution, in mixed solution, add milk of lime to carry out causticizing reaction, the add-on of milk of lime is 42% of desiliconization liquid volume after mixing, obtain the wollastonite slurries, to wollastonite slurries separating, washing, obtain solid silicon lime stone and NaOH solution, using the NaOH solution that obtains as circulation NaOH solution, with return to initial step and mix with flyash, to the solid silicon lime stone, add the milk of lime that accounts for solid silicon lime stone volume 8.0% to carry out dealkalize, then adopt the acetic acid pickling, after the control pickling, the wollastonite pH value is 7.1, stops 10h in 230 ℃ of insulations, then, after drying, obtains the wollastonite product,
(2) the two-stage desilication slag is mixed with circulating mother liquor, add ferrous acid sodium and milk of lime, in 280 ℃ at Leaching reaction 1.5h, to the leaching slurry obtained diluted, after separating, washing, obtain solid water garnet and dissolution fluid, after the solid water garnet is carried out to the separating, washing oven dry, obtain iron hibsehite product; Described ferrous acid sodium add-on control mode is: Fe in ferrous acid sodium
2o
3al in/two-stage desilication slag
2o
3mass ratio is 0.7:1, and described milk of lime add-on control mode is: Al in CaO/ two-stage desilication slag in milk of lime
2o
3mass ratio is 2.0:1;
(3) add milk of lime in the dissolution fluid in step (2), in 185 ℃ of stripping reaction 1.0h, obtain the tricalcium aluminate slurries, the tricalcium aluminate slurries are carried out to solid-liquid separation, obtain tricalcium aluminate filter cake and tricalcium aluminate parting liquid, the tricalcium aluminate filter cake is washed, obtained tricalcium aluminate and tricalcium aluminate washing lotion; Described milk of lime add-on control mode is: Al in the CaO/ dissolution fluid in milk of lime
2o
3mass ratio is 1.5:1;
(4) tricalcium aluminate is mixed with the carbon mother liquid after evaporation, in 182 ℃ of reaction 1.2h, obtain calcium carbonate serosity, after the calcium carbonate serosity separating, washing, obtain calcium carbonate filter cake and parting liquid, in parting liquid, continue to pass into CO
2carry out the carbonating decomposition
,the carbonating obtained is decomposed slurries after filtering, obtains aluminum hydroxide filter cake and parting liquid, and filter cake, through washing, obtains aluminium hydroxide solid and aluminum hydroxide wash liquor, after the aluminium hydroxide solid is dried, obtains finished product ultrawhite aluminium hydroxide; Described CO
2the add-on control mode is: pass into CO
2al in/parting liquid
2o
3mass ratio is 1.4:1.
Described tricalcium aluminate parting liquid and the tricalcium aluminate washing lotion mixing that accounts for tricalcium aluminate washing lotion cumulative volume 64%, NaOH concentration 280g/l in the evaporation control mixed solution, enter in step (2) and carry out Leaching reaction as circulating mother liquor; Remaining 36% tricalcium aluminate washing lotion is returned in step (1) and is mixed with aluminous fly-ash.
After mixing, the parting liquid that described carbonating decomposition slurries obtain after filtering and aluminum hydroxide wash liquor as carbon mother liquid, carbon mother liquid is evaporated to Na in solution
2cO
3concentration is 145g/l, obtains mother liquid evaporation and solid sodium carbonate, and described mother liquid evaporation returns in step (4) and mixes with tricalcium aluminate, and described solid sodium carbonate mixes with iron filings, at Na
2cO
3/ Fe
2o
3weight ratio is 0.64:1, and roasting under 850 ℃ of conditions, obtain ferrous acid sodium, enters in step (2) and carries out Leaching reaction.
Described calcium carbonate filter cake adds in 95 ℃ of hot water after 1000 ℃ of lower roastings carries out lime slaking, is prepared into qualified milk of lime, enters in step (1), step (2) and step (3).
Claims (4)
1. the method that aluminous fly-ash high temperature alkali soaks production ultrawhite aluminium hydroxide and byproduct is characterized in that carrying out according to following steps:
(1) aluminous fly-ash is milled to below granularity 200 orders, mixes Al in mixed solution with circulation NaOH solution and tricalcium aluminate
20
3concentration is 13 ~ 14g/L, and α k=30 carries out one section atmospheric silicon removing 0.5 ~ 1.0h in 80 ~ 105 ℃
,obtain one section desiliconization liquid and one section desiliconization slag, then at 130 ~ 160 ℃, 0.27 under the condition of ~ 0.62MPa, one section desiliconization slag is carried out to pressure-off silicon 0.5 ~ 1.0h in two sections, obtain two-stage desilication slag and two-stage desilication liquid, one section desiliconization liquid is mixed with two-stage desilication liquid, in mixed desiliconization liquid, add milk of lime to carry out causticizing reaction, the add-on of milk of lime is 38 ~ 42% of desiliconization liquid volume after mixing, obtain the wollastonite slurries, to wollastonite slurries separating, washing, obtain solid silicon lime stone and NaOH solution, using the NaOH solution that obtains as circulation NaOH solution, with return to initial step and mix with flyash, to the solid silicon lime stone, add the milk of lime that accounts for solid silicon lime stone volume 5.0 ~ 8.0% to carry out dealkalize, then adopt the acetic acid pickling, after the control pickling, the wollastonite pH value is 6.9 ~ 7.1, stops 8 ~ 10h in 230 ~ 280 ℃ of insulations, then, after drying, obtains the wollastonite product,
(2) the two-stage desilication slag is mixed with circulating mother liquor, add ferrous acid sodium and milk of lime, in 230 ~ 280 ℃ of Leaching reaction 1.5 ~ 2.5h, to the leaching slurry obtained diluted, after separating, washing, obtain solid water garnet and dissolution fluid, after the solid water garnet is carried out to the separating, washing oven dry, obtain iron hibsehite product; Described ferrous acid sodium add-on control mode is: Fe in ferrous acid sodium
2o
3al in/two-stage desilication slag
2o
3mass ratio is (0.5 ~ 0.7): 1, and described milk of lime add-on control mode is: Al in CaO/ two-stage desilication slag in milk of lime
2o
3mass ratio is 2.0:1;
(3) add milk of lime in the dissolution fluid in step (2), in 180 ~ 185 ℃ of stripping reaction 1.0 ~ 1.5h, obtain the tricalcium aluminate slurries, the tricalcium aluminate slurries are carried out to solid-liquid separation, obtain tricalcium aluminate filter cake and tricalcium aluminate parting liquid, the tricalcium aluminate filter cake is washed, obtained tricalcium aluminate and tricalcium aluminate washing lotion; Described milk of lime add-on control mode is: Al in the CaO/ dissolution fluid in milk of lime
2o
3mass ratio is 1.5:1;
(4) tricalcium aluminate is mixed with the carbon mother liquid after evaporation, in 180 ~ 185 ℃ of reaction 1.0 ~ 1.5h, obtain calcium carbonate serosity, after the calcium carbonate serosity separating, washing, obtain calcium carbonate filter cake and parting liquid, in parting liquid, continue to pass into CO
2carry out the carbonating decomposition
,the carbonating obtained is decomposed slurries after filtering, obtains aluminum hydroxide filter cake and parting liquid, and filter cake, through washing, obtains aluminium hydroxide solid and aluminum hydroxide wash liquor, after the aluminium hydroxide solid is dried, obtains finished product ultrawhite aluminium hydroxide; Described CO
2the add-on control mode is: pass into CO
2al in/parting liquid
2o
3mass ratio is (1.2 ~ 1.4): 1.
2. the method that a kind of aluminous fly-ash high temperature alkali according to claim 1 soaks production ultrawhite aluminium hydroxide and byproduct, the tricalcium aluminate washing lotion mixing that it is characterized in that described tricalcium aluminate parting liquid and account for tricalcium aluminate washing lotion cumulative volume 60 ~ 65%, NaOH concentration 260-280g/l in the evaporation control mixed solution, enter in step (2) and carry out Leaching reaction as circulating mother liquor; Remaining 35 ~ 40% tricalcium aluminate washing lotions are returned in step (1) and are mixed with aluminous fly-ash.
3. the method that a kind of aluminous fly-ash high temperature alkali according to claim 1 soaks production ultrawhite aluminium hydroxide and byproduct, it is characterized in that described carbonating decompose parting liquid that slurries obtain after filtering and aluminum hydroxide wash liquor and mix after as carbon mother liquid, carbon mother liquid is evaporated to Na in solution
2cO
3concentration is 140 ~ 150g/l, obtains mother liquid evaporation and solid sodium carbonate, and described mother liquid evaporation returns in step (4) and mixes with tricalcium aluminate, and described solid sodium carbonate mixes with iron filings
,at Na
2cO
3/ Fe
2o
3weight ratio is (0.661 ~ 0.664): roasting under 1,800 ~ 900 ℃ of conditions, obtain ferrous acid sodium, and enter in step (2) and carry out Leaching reaction.
4. the method that a kind of aluminous fly-ash high temperature alkali according to claim 1 soaks production ultrawhite aluminium hydroxide and byproduct, it is characterized in that. described calcium carbonate filter cake adds in 90 ~ 100 ℃ of hot water after 950 ~ 1050 ℃ of lower roastings carries out lime slaking, be prepared into qualified milk of lime, enter in step (1), step (2) and step (3).
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